Process for decolorizing a soybean oil miscella



Patented Aug. 26, 1952 UNITED STATES PATENT OFFICE PROCESS FOR DECOLORIZING A SOYBEAN OIL MISCELLA Ralph A. Marmor and Wendell W. Moyer, Decatur, Ill., assignors to A. E. Staley Manufacturing Company, Decatur, 111., a corporation of Delaware.

No Drawing. Application June 17, 1947, Serial No. 755,253

2 Claims. ((31.260-427) 1 i 2 This invention relates to improvements in the refined qualities could be maintained during manufacture of glyceride oils. More specifically, reasonable period of storage. For example, 001']:-

it pertains to improvements in the production of ventional freshly refined soybean oil is an excelsolvent extracted crude glyceride oils which, when lent edible oil. Without further treatment, it refined y ve al methods and ut l ng is quite suitable for the preparation of salad novel low temperature removal of solventcomdressings, and when properlyhydrogenated it bmed w th a decolorizing step, yield refined oils makes an excellent shortening and margarine 'oil. of superior qualities. The flavor and odor stability characteristics of V A ary object of the invention is to p vi the conventional refined soybean oil, however, are the production of yceride O ls vin less than those of other competitive edible oils. proved r, v r, r, an r sis an o r The refined oil, either alone or in combination Version and development of O da Ve ra o dity with other food materials, rather rapidly develops during Storage substantial oxidative rancidity and noticeable Another object of the invention is to provide a fiavor reversion. The rancidity is measurable as novel treatment of the oil prior to conventional a peroxide value. To prevent this, so as to per. refining p o s le using alkalies and elemit use of the refined oil in foodstuffs, it has here- Vated temperaturessuch t e refi d Oil is tofore been necessary either to give the oil an m y i p v d with r sp t to color, flav additional and special refining treatment or to odor, and resistance to reversion and developr at it with suitable stabilizers. ment of OXidatiVe ranoidity during Storage The present invention provides a process for A further object Of the invention is to eliminate the preparation of refined solvent extracted 50ythe need for treating the oil with color adsorbents bean 11 d other glyceride 11 which m;

after thecustomary alkali treatment to remove ciently t ble to be used in stored foodstufis' u and acidswithout additional refining or treatment with A t r j t f the invention is to provide stabilizers. This is accomplished by separating 1 the production of Partially Solvent the solvent and oil at temperatures substantially extracted glycerlde oils having improve 00101, below those used heretofore andsubjecting the fiavorand Odoroil to the action of a color adsorbent prior to Additional Objects of the invention will be other refining operations. The order in which apparent from the following descriptiim' and the solvent is removed and the oil is contacted 9 with a color adsorbent does not materially affect The V F accorfimgly compnses the the qualities of the final oil. We prefer to treat era'l 3 and the relatlon Drone more of Such the solution of oil in solvent, either as a full or steps wlth respect to each of the Others thereof partial miscella, with the color adsorbent first,

which will be exem lined in the recess hereinafter disclosed andpthe scope of li application mainly because such solutions are less viscous than the undiluted oil and are more easily perof which will be indicated in the claims. I

1 colated or filtered through a bed of the adsorbent Nearly all refined glycende 011s of .edlble g1 i material. However, the advantages of this inven develop some undesirable flavor or odor during tion can be obtained by first evaporating he prolonged storage. The degree to which this r 40 solvent from the extracted 011 at low tempera occurs depends upon the kind of 011, the nature of tures, and then contacting the on with a to 0101,

the. refinin rocess, and the conditions of v storage Ot her conditions being equal the m dsorbent, either in the absence or presence of a diluent.

saturated the 011 the more stable 1t 15, in general, We have discovered that conventional refining to storage. Light and oxygen generally accelerate the deterioration of the stored oil. Freof Solvent extracted glyoeride 11s y s final oils quently, the refined oil, either as such or as an of markedly Superior qi s f, p i r o any hydrogenated oil, is stored as an ingredient of a other conventional refining Operations, the 011 S foodstuff, such asmargarine, salad dressing and contacted with a color adsorbent and the solvent shortening. Obviously, any appreciable developis removed from the oil, b01311 Operations b g mentof rancidity or other off-flavor or odor in p s d at mp ratu s not e c d such foodstuff is highly undesirable. about 50 C. It is the combination of low tem- 0vving to such deterioration during storage, perature solvent removal and color adsorbent some readily available glyceride oils are not as treatment, prior to other refining operations; that widely used in the preparation of the above menis important. As mentioned earlier, the order in tioned foodstuffs as they would be if their freshly which the two steps of the combination are per"- formed has no appreciable effect on the quality of the final oil. Prevention of thermal degradation of the color bodies and other materials are believed to be responsible for stability characteristics 'of 'the oil; *The qualities of the oil that are markedly improved by our invention are those of color, flavor, odor and stability towards reversion and development of oxidative rancidity during storage.

We have also found that the V decolorizecl crude oil obtainsdinaccordance'with our invention is very light colored and possesses Any of the conventional oil color adsorbents are suitable. Following this, the oil is winterized, i. e., stored at low temperatures and then filtered to remove precipitated solids, if the oil is to be used under temperatureconditionslikelyto cause separation'of'iwaxes and-other high" melting eonstituents. The final steps in the conventional refining of crude glyceride oils are deodorization and check filtration. Deodorization usually consists' of--passing-*superheated steam through the hot oil under high vacuum. This treatment removes-disagreeableodorous constituents of the oil remaining from the preceding refining operations:

quality of the final product are provided-by this combination, however, even though subsequent 'refin'ingl'zoperations do not includea'an alkali treat- 'ment."v

r The: currentlyrpr'eferr'ed' solvent for the "corn"- mercial extraction of glyceri'de oils is so-called hexane," a-f high' test gasolineboiling" over a range of about"63to "70 C; "Such solvents astrichloroethylene',' benzene; and. ethanoL'allhaving boiling points2under'90 C1; are also used.

. 'Bri'eflyreviewingithei solvent extraction-of: oil fionruai raw'material, such :as soybeans rfo'r "examplej thefiusual commercial? practice: is' to fiak'e the-cracked 'beansf and-then leach the oil from them with hexanesolvent. This issaccomplished either by percolating the solvent through stationary bed" iofith'e flakes;"or by washing the flake-s coufitercurrentlyitvith thisolvent in as'pecial "apparatus; The" solution for oil 1 in: hexane, known as full' miscella andic'ommo'nly containing about three parts of solventto 'one'part *oil'j'is' distilled at atmospheric. pressure to remove most of the solvent from the 011. Temperatures attained by the 'oil solvent mixtureiini thi S7015 eration conven- 'tiona'lly ra'nge from about 60 to 90 C. The solvent-remaining .in the oil is then removed under "v' uum at temperatures rangin from-about 100 toil-' C.

The c'rude -oil obtained? as describedabove is therrirefinedor purified. The chief impuritiesin crude soybeanioihvas well. .as crude glyceride oils in -general; "are" gummy materials; consisting mainly of .phosphatides; andfree fatty acids. -f'mpurities "present" in lesser proportions are-color bodies, waxes, unidentified disagreeable odorous constituents;sterols,- and other materials; The gummy -materials andfree fatty acids. are conveniently andcommonly. removed-bystirring the warm crude'oilvigorously with a proportion-"of moderately strong aqueous solution; of caustic sodaslightly in'eXcess-of that required to combine-.withthe-acidic: impurities, and. then separati'n the oily and aqueous phas'eseitlier' by gravity settling and decantation or by centrifuging. The aqueous phase carries with it thefg'ums and free fatty acids, the former as an intimately dispersed and partiallyTsaponified material, and the latter. as a' solution of" dispersion of the sodiumsalts-or soaps. Residual soap'andfree alkali in these'parated oil are rein'ov'edby washing the'oilfwitli water. The next. conventional refining operationis bleaching or'decolorizing to reduce thecolor of the" crude oil. This usually consists. o'fistir'ring thewarm oilwith'a color ad'- slorbent'such as activatedc'arbon, alumina, mag

nesia' clay, etc. ,.and'filteri'ng themixtur'e toremove. the adsorbent andadsorbedirnp'urities.

There are many known variations of the above described process for refining crude glyceride oils. For example; the crude oil may be degummed beforeit is treated with alkali. This usually consists/of vigorously stirring the warm oil with about two or three per cent of an aqueous medium,-. consisting optional-1y .of water-v alone, dilute-acid, dilute alkali, orsalt solutiomwhich hydratesthe gum or phosphatides and precipitates them-from-the oil, andthenseparatingsgum irom-oil, eitherbygravity settling. and decantationor'by centrifuging. The degumming. maybe performed. onflthe -crudev oil alone oron-Jtheoil dissolved in some solvent. Too .much -solvent,

however,interferes somewhat with separation of the hydratedgum. ;Other-. alkalies or alkaline materials-may be substituted forthecaustic-soda in the alkali treatment. In some instances, where water degumming is employed, thelalkali -streatmentsis eliminated- In. others.-the.. -or.der1v of bleaching, interizing 1 (if, used) and deodorization described above is altered Regardless ofthe mannerfin which the glycer-ide oil-is. conventionally refined, priorlow temperature contact ,of thez-oil with a .co-lonadsorbent andtl-ow tempera ture removal ore-solvent from oillin accordance withour invention will. markedly. improve .the quality-of-therefined oil.

In .the preferred practice ofsour invention the full miscella is stirred with a coloradsorbentat temperatures .not exceeding ab0ut50 C. until color adsorption .reaches substantial equilibrium. This usually-does -notreq.uire more than about one hour. The mixture is then-filtered to remove the adsorbent, and the: filtrate T is; evaporated un'derlreducedepressure and ata maximum temperature of 50 C. until no more thaniabout one or two per cent ,of solvent remains in the :oil. The vaporized-solvent may-be recovered-by con:- veying it -toa-anlefiicient surface'condenser. We have/observed; that removal of the last fewzper cent of solvent from=the :oil at-temperature not exceedingabout 50 .C. isaslow, even though very low pressures-be used. It is, therefore, advantageous to leave aboutlonewper. cent or so-ofz-sol- .vent in the oil,"thisrpercentagebeing basedon the ,oiland not on the solvent initiallyzpresent in the'misc'ella. This residualsolvent isicompletely removed in x the subsequent refining. operations, and it does-"not .interfere'with those operations. Loss for" such residua'l solvent is not uneconomical when it is-compared with the-benefits of the invention.

Next the decolorized *and low-solvent-content oil-is degummed-Witn water'in a conventional manner, preferably, however," attemperatures not exceeding about 50 C. Following thisfthe oil is alkali refined inaconventional manner. The crude phosphatidic'gum obtained in the first operation is-much lighter coloredthanusual: This is due'in' part to the 'prior"decolorizing' treatment and in part to the low temperature .s The following examples willtmorefullyillustratethe invention: 1 I a Example 1 i Six liters of a full miscella consisting of about one partsoybeanroil, and three parts hexane was agitated-with about-30 grams of an acid activated bleaching clay for about one hour at 25 to 30 C. The mixture was filteredto remove the clay and the noticeably decolorized filtrate was vacuum distilled at a maximum temperature of about 50 C. until the residual oil contained only about two per cent'fliexana?Thisoil was next stirred vigorously at 50 C. with about two per cent water and" allowed to stand until the hydratedgums semester; 'Thsupernatant oil was decanted from the gums and alliali refined in conventional manner at a maximum temperature of; 70 C. gag ng a 0.25 er cent excess}. of aqueous, 16 Baum sodiumhydroxide solution. The soapstock was allowed to -settle by gravity from the alkalitreated-oil. l. The supcrnatantoil was decanted from thefoots, washed with water to remove traces of soaps and free alkali, and then deodorized by vacuum steam distillation with superheated steam in a conventional manner.

Example 2 Same as Example 1 except that the acid activated clay was replaced with an activated vegetable carbon.

Example 3 Same as Example 1 except that the acid activated clay was replaced with an activated adsorbent grade of magnesia.

Example 4 Same as Example 1 except that the acid activated clay was replaced with an activated adsorbent grade of alumina.

Example 5 Six liters of a full miscella consisting of about one part soybean oil and three parts hexane was agitated with 0.02 part of an acid activated clay for about one hour at 25 to 30 C. The mixture deodorized'by "vacuum steam distillationcwith superheated steam. in a conventional manner.

E m le r Same as Example 5 except thatthezacid-activated claywas replaced 'withan activatedve'getablecarbonn M a 1 1 1 Example 7 Same as Example 5 exceptthattheacid acti'- vated clay was replaced with an activated'mag} nesia. V v

- Example 8 v. Z=iame as Example 5 except that the acl d .activated clay wasv replaced with an activated alumina." I I mmr 9 1 Same as Example 2 except thatthe soybean oil was replaced with corn oil.

Example 10 Same as Example 6 except that the soybean oil was replaced with corn oil. i Samples of the refined oils obtained in the foregoing examples were stored in diffused light at 25 to 30 C. Control samples of the refined oils were stored under the same conditions. The controls were prepared as described in the examples except that the solvent was removed from the oil at the conventional higher temperatures of about to 100 C., and the oil was decolorized after the alkali treatment instead of before it. Comparisons were made immediately and after 21 day storage of color, odor, flavor, and peroxide value. In every instance it was found that the color, flavor, odor at room temperature, odor at 426 F., and resistance to reversion and de velopment of oxidative rancidity of the oils treated as described in the examples above were markedly superior to those properties of the corresponding controls. Samples of the crude decolorized oils obtained in the foregoing examples were also compared immediately with the crude controls for flavor, color and odor. The results tabulated below for Example 1 and its controls are illustrative of the results obtained in the other examples:

Treated Oil Bleaching of Miscella plus Low Temperature Removal of Solvent Example 1 Control 1 Immediate Color l0yl.0R. Immediate Flavontrace raw. Immediate Odor.... trace been. Immediate Heat Odor--- Sharp and grassy. Immediate Peroxide Value 0.10.

Color after 21 days storage.. Flavor after 21 days storage.. Odor after 21 days storage Heat Odor after 21 days storage.

Peroxide Value after 21 days storage...

trace paint.

. trace paint.

strong paint or soybean reversion.

v. f. very faint.

S1. slightl was filtered to remove the clay, and the noticeably decolorized filtrate was vacuum distilled at a maximum temperature of about 50 C. until the residual oil contained only about two per cent hexane. This oil was next alkali refined in conventional manner at a maximum temperature of 70 C. using a 0.25 per cent excess of aqueous 16 Baum sodium hydroxide solution. The soapstock was allowed to settle by gravity from the alkali treated oil. The supernatant oil was decanted from the soapstock, washed with water to remove traces of soap and free alkali, and then glyceride oil is suitable for the purposes of our invention:'Itis-v tobe understood thatmany dirbeinterpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all of the generic and-specific features of the invention herein described,-'-and all statements of the scope'of the invention which, as a matter of 1anguage;-might be said to fall therebetw-een;

' Weclairn:

1. In the process of refining soybean oil obtained by extracting the oil from soybeans with hexane solvent, the "improvement comprising the sequentialstepsxof contacting the extract with a color adsorbent at'atemperature below about 50"; C.,-.and subsequently removing the solvent from the extract by vacuum distillation at a'temperature' below -=about 150 1 0.; before-any .additional refining steps.

2.'The:-improvement called for" in claim 1 wherein said vacuum distillation step is-terminated so as to leave aresidue of approximately 1% of the solvent in said soybean oil, based on the weightgofthe oil;

" RALPH A. MARMOR "WENDELL' W; MOY ER;

REFERENCE Sf CITED- The following references are, of frecordglngthe -file .of this patent:

D-1' ST S PAT T OTHER REFERENCES Buxton Industrial 83 Eng. Chemistry; December 1942, v01. '34; No. 12, pp.-1486-7. 

1. IN THE PROCESS OF REFINING SOYBEAN OIL OBTAINED BY EXTRACTING THE OIL FROM SOYBEANS WITH HEXANE SOLVENT, THE IMPROVEMENT COMPRISING THE SEQUENTIAL STEPS OF CONTACTING THE EXTRACT WITH A COLOR ABSORBENT AT A TEMPERATURE BELOW ABOUT 50* C., AND SUBSEQUENTLY REMOVING THE SOLVENT FROM THE EXTRACT BY VACUUM DISTILLATION AT A TEMPERATURE BELOW ABOUT 50* C., BEFORE ANY ADDITIONAL REFINING STEPS. 